Preparation of amine hydrohalides



July 9, 71935;

A. 1.-.. FOX

PREPARATION OF AMINE HYDROHALIDES Filed May "6, '1-932 s Sheets-Sheet 1'ATTQRNEY.

July 9,1935. A, L. FOX 2,007,189

PREPARATION OF AMINB HYDROHALIDES I Filed May'6, 1932 5 Sheets-Sheet 5F' m I 1001 F Fu fi- Fi lO A L I 'INVENTOR.

I ur ox,

BY J

ATTORNEY.

Patented July 9,1935- p 2,007,189

UNITED STATES rAT -NroFncE 2,007,189 v PREPARATION or AMINEHYDROHALIDES" Arthur Lawrence Fox, Wilmington, DeL, assignor to E. I duPont de Nemours '8; Company, Wilmington, Del., a corporationof DelawareApplication May 6,1932, Serial No. 609,741

' 13 Claims. (01. zoo-130.5)

This invention relates to the preparation of zone whose temperature isgreater than the boilorganic compounds and more particularly to the ingpoint of the amine and preferably in a zone preparation of aminehydrohalides. whose temperature is greater than the boiling In the pastamine hydrochlorides havevbeen point of the resultant amine hydrohalide.The

' prepared by the reactions carried out with hydroinvention will befurther understood from a con- 5 chloric acid in aqueous solutions. Inorder to sideration of the accompanying drawings and isolate the aminehydrochloride producedby such the following description which includesseveral a process it has been necessary to either concenspecificexamples. In the examples the parts are trate (for example, byevaporation) the solution given by weight.

l or salt out'(for example, with an excess of hydrohe p ess f th V Q iadva age us y practical results were not obtainable' chloric acid) thedesired product. This process carried out using apparatus such as thatillushas not been commercially desirable in general trated in theaccompanying drawings in which because of the'great solubility andhygroscopic imilar num r l r f to mila part hr hcharacter of aminehydrochlorides. i Ordinarily out the several viewsand descriptionthereof.

' i In the drawings: 7 i 15 An improvement over the above mentioned 1isa sideview partly in section and someprocess is described by Ahlum inU. s. Patent" what diagra ma f n m f pp r f r 1,303,624 of May 13, 1919,according to which a. ying out the invention.

. dry amine (for example, aniline) and dry hydro- 7 Figs 3 and 4 aresomewhat similar views of gen chloride gas are reacted in the presenceof a difi S' the atOmiZing dev 7 "20 non-aqueous solvent (for example,benzene). I 5 S V w partly in section and S e- 7 Even with this processdifiiculties are encountered What diag a matic of amodified form ofamine in the'filtration-of certain amine hydrochlorides y o ldecollection chamben.

from th l nt Fig.6 is a side view partly in section and some- 725 It hasnow'beenfound thatq'uantitative yields Wha d agrammatic of a modifiedform of reacof substantially pure amine hydrohalides in very .tionchamber, g V v desirable physical form may be prepared'in' the Fig. 7 isan elevation of an apparat 3 ca r absence of a solvent by bringingan'atomized or ing Out the i venti n on a small scale. I vaporizedanhydrous amine into contact with an- 1 Fi 9, 10 and 11 are elevationsof parts of t hydrous hydrohalide vapors under such condi d fi d formsOf the pparatus shown in Fig. 7. 30

tions thatthe reaction of the two takes place in n gene al, thisinvention involves atomizin a zone whose temperature is higher than the.0 vap g an am an Contactin it i at boiling point of theiamine.'Dhysicalstate with a hydrogen halide gas and This inventicnhas for anobject the preparacollecting the amine hydrohalide formed. One

tion of amine hydrohalides me, very desirable form of apparat s OIatOmiZing O vap i 35 physical form, and by a commercially feasible theamine is indicated in the drawings generally process. Other objects arethe preparation of by the letter A. The atomized amine may be conaminehydrohalides under anhydrous conditions, Veniently contacted with thehydrogen halide gas' their preparationin theabsen'ce oi a'solvent, insuch an apparatus as generally indicated in E their preparation by meansof hydrogen halide Fig. 1 by the letter B. Theresultant amine hy- 40gases, their preparationby means of the interacdrohalide may becollected in anysuitableform ticn of a hydrogen halide gas and anatomized of apparatus. One specific form is indicated genamine, theirpreparation by the interaction of a erally in Fig. 1 by theletter'C.- V

hydrogen halide gas and a vaporized amine, their Referring to Fig. l ofthe drawings, l indicates 7115 preparation by the interaction of ahydrogen a reservoir or kettle containing a supply of an halide gasandan amine at a temperature above amine indicated at 2. This'reservoiris supported the boiling point of the amine, their preparation uponupright columns such as that indicated by by the interaction of ahydrogen halide gas and the numeral 3 and there is provided a gas burneran amine at a temperature abovethe boiling 4 whichmay be used forheating'the kettler A point of the resultant amine hydrohalide and insupply of gas for the burner 4 is furnished bypipe general .an'advancement of the art, Other obline 5. The container has a bottomoutlet 6 and jectswill appear hereinafter. V a device generallyindicated at! forindicating The above mentioned objects are accomplishedthe level of the liquid therein. by atomizing or vaporizing an amine andcon- The indicating device 1 consists of a transpar- V tacting it with agaseous hydrogen halide in a ent housing 8 (glass or the like), mountedon the 55 the like) which is indicated at 2|.

closed by a closure plate indicated at 58.

ceiving chamber I02. into this chamber around bailie plate I03 andinto'a second receiving chamber I04 through an opening generallyindicated at I05.

top of the kettle and an indicating rod 9 movably mounted in the housing8 and supported by a float I resting on top of the liquid in the kettle.The reservoir may be filled with a liquid amine by means of an inletpipe II, through valve I2 and pipe I3. A large opening I4 is arranged inthe top of the reservoir for the introduction of solid amines. A supplyof air or other inert gas under pressure (not shown) is connectedthroughpipe I5, valve I6 and line I3 to the kettle. By proper regulationof the valve I6 the contents of the kettle are placed under sufficientpressure to force the amine through line I? into a spraying devicegenerally indicated at I8. 7 I

This atomizing device involves a'distributing part I9 and an outer platesection 20. In order to keep the amine at constant temperature that partof the pipe I! which extends from the reservoir I to the distributingpart I9 of the nozzle is cov--' ered with heat insulating material(asbestos or Thespray plate 20 has a hollow cylindrical extension 22thereon for conducting the atomized or vaporized amine into'the reactionvessel This reaction vessel has a bottom outlet through valve 52 and aside outlet through pipe line 53.

Its outer surface is lagged with some heat insulatingmaterial asindicated at 54 for maintaincal pipe" 56 which surrounds the aforesaidspray 'plate extension.

Entry to the pipe 50 is had through the line 51 which line is connectedwith a sm'table source of dry hydrogen halide.

An opening in' the top of the reaction vessel is Tn lagging on thereaction chamber also extends over the exit pipe 53. I

The amine hydrohalide formed leaves through pipe 53 and passes throughthe cross 59, into the This receiving apparatus involves an inlet pipeIOI connected with the cross 50 and with a re- The material passes downDuring its passage through chamber I02 and around baffle plate I03 mostof the amine hydrohalide'settles out.

Most of the remaining amine hydrohalide settles out during its passagearound a baiiie plate I06 in chamber I04. Any remaining aminehydrohalide passes through opening I01 into a third receiving chamberI08 containing a baifle plate I09 where it settles out. Outlet IIOhaving a closure I I I- permits the escape of gases when the apparatusis operated under such conditions that pressures in excess ofatmospheric exist in the receiver I08. Each of the receiving chambershas flexible nozzles H0, H9 and I20. The containers I02, I04 and I00 aresupported by means of vertical beams I2 [and 122 and horizontal beamsI23 and I24.

In Fig. 2 another i'orm of atomizing device is disclosed. This deviceincludes-a pipe 20! through which the amine enters. The amine escapesthrough a small opening 202, the size of. which is regulated by a needle203 which is regulated by means of a handwheel 204 and a screw 205.

Another form of atomizing device is disclosed in Fig. 3. In this figurethe amine enters the device through line 30I and is blown into a sprayby a jet of air or other inert gas entering through the line 302. Thespray leaving the atomizing chamber generally indicated at 303 passesthrough an extension thereof made of glass or other transparent materialand indicated at 304 into the reaction chamber which is not shown inthis figure. By having the atomized amine pass through a section 01transparent material the character of the jet of atomized material maybe observed. Suitable regulation of the jet may be made from theinformation thus obtained. In the device shown the inlet pipe 30I passesthrough a body of packing material 305. iStill another form of atomizingdevice is disclosed in Fig. 4. In this figure a stream of amineindicated at 40I enters through line 402. At the point generallyindicated at 403 it is disintegrated by a blast of air or other inertgas entering through line 404. The gas entering is regulated by means ofa valve 405 between the line 400 and the line 406 which line (400) isconnected with a suitable source of gas under pressure. In certaininstances it may be desirable to add a hydrogen halide as or with theatomizing gas. l orv this reason the line 401 and valve 400 areprovided. A suitable source of a hydrohelide gas is connected throughline 400 to the valve 408.

In Fig. 5' there is shown an alternative form of collection chambergenerally indicated'at 50!. The collection chamber except for the bottom562 which is covered with brick is lined with some corrosion-resistantmaterial (lead or the like) generally indicated at 503.. This chamberhas doors such as indicated at 504 and 50 through which the aminehydrohalide may be removed as desired. Forthe purpose of facilitatingthe settling of the amine hydrohalide, baiiies 505 and 501 are providedon the interior of. the chamber 50I. Under certain conditions ofoperation it may be desirable to maintain the collection chamber undersubatmospheric or superatmospherlc pressure. For the purpose ofmaintaining reduced pressure therein a suction device mounted on a base509 is provided. This suction device is connected through valve 550 andline 5 to the chamber 50I. Superatmospheric p sure may be produced inthe collection charmer by closing or throttling the valve 5 I 0.

A gauge 5I2 is connected to the chamber in the vicinity of the line 5|I, for the purpose of indicating the pressure within the chamber. Asfurther shown in Fig. 5, a vent 5I3 having a closure 5I4 is provided.-An adjustable lever and weightarrangement.indicated at 515 limits thedegree of superatmospheric pressure in the collection chamber bypermitting the escape of gases through the said vent. As will be clearthe weight may be moved along the lever to any desired position.Obviously the nearer the weight is to to the closure 5I4 the lesschamber pressure required to open the said closure. The collectionchamber has an inlet generally indicated at 5! 5. This inlet comprises acentral heat and corrosion-re sistant material (for example, tantalum,special corrosion-resistant steel or some vitreous substance) generallyindicated at 5I'I around which is located some heat resistant material548 (for example asbestos, kieselguhr or the like) A heating coil 519surrounds the part 5| 1 and is embedded in the part 5|8, which materialin turn is 'located within a-metallic shell shown at 520. On

the interior of the chamber to! between the shell 52!) and the lining503 there is another body of heat-resistant material (for example, brickor the a the amine and which is concentric about a smaller pipe 604through whichthe hydrohalide gas enters..

As shown in the figure the end of the hydrohalide gas'li'ne sue extendsinto the reaction chamher but if desiredthis may be flush with the sideof the cylindrical jacket 50! .or the same may terminate within theamine entry line 503. The

reaction chamber is surrounded by a heat resistproper temperature.

ant material-M3535 and has a top closure generally indicated at set. Thebottom of the reaction chamber is indicated at (Sill. For the purpose ofmaintaining proper temperatures withinthe reaction chamber an electriccoil 6% is provided for heating the walls thereof. This heating element668 is embedded in the heat insulation material surrounds the exit 6%.as well as the main portion of the reaction chamber.

In" Fig. '7 there is illustrated ,a device for carrying out theinvention on a small scale. This comprises an amine reservoir 'HH havingan outlet through line 'lElZ. This" line extends intoan atomization orvaporization chamber 103. A gas line 1% extends into the atomization orvaporization chamber. This line supplies the air or other gas whichcauses the atomization and vaporization of the amine. A combinedcollection and reaction chamber is illustrated at. I05. The atomizationand vaporization chamber extends into the atomization or, vaporizationchamber. figure the atomization chamber 8fi3 is sealedas indicated at882 by a closure means 80!. The modification illustrated in this figureis advanthis chamber. g

H A line tilt is provided for the admission of the hydrohalide gas. .Theline we terminates adjacent the end of the atomization or vaporizationchamber Hi3. In operation the reaction takes.

place in this zone and the amine hydrohalide formed settles to thebottom of the container 105. An outlet Nil for the escapeof thegasentering through line N34 is provided. If desired the outlet Mil maybe connected to a vacuum producing apparatus for the facilitation of theremoval of the air or other gas previously referred to.

In Fig. 8 there is illustrated almodification in Inthis tageous whereitis desired to maintain specific pressure conditions within the chamber893*.

Under certain instances it is desirable to force the amine into theatomization or vaporization 'inthis figure the atomization-andvaporization chamber 903 is closed at 902 by a closure means el. Theamine reservoir is'closed at '904 bya "drogen halide.

closure means SOS'through which a line 906 extends. 'Air or any desiredgasmay be forced through the line 9% resulting in the forcing of theliquid amine generally indicated at 90! out through the line 908 intothe atomizattion and vaporization chamber 903. v I A modified form ofatomization or vaporization chamber is illustrated in Fig. .10. In thisfigure the main chamber I693 has an outlet at I 082 through which anyunvaporized or atomized amine'which might collect in the portion Hlillof the atomization and vaporization chamber limit may escape. I Asdescribed in the apparatus previously mentioned, the amine may bepreheated by the application of heat to the amine reservoir. It has beenfound" advantageous in certain instances to preheat the gas used for'atomizing and vaporizing the amine and a form of apparatus foraccomplishing this result is illustrated in Fig. 11. In that figure thegas for atomization or vaporization of the amine enters through openingHill andpasses through coil H82. After leaving this coil the gas entersthe atomization or vaporization chamber H 33 in-the same manner asillustrated in Fig. I through line 'i it. Surrounding the coil portion llfiZ is a vessel W35 having an inlet H06 and an outlet at Hill.

Hot liquids or gases (for example, the gases escaping from the reactionand gas in the coil t2 andpass out through the outlet i iiil.

In the small scale apparatus last described the .atorcizing-gas jetpassing over the line from the amine reservoir causes the amine to bewithdrawn from the line in ordinary instances. However, as stated above,pressuremay be employed to force the amine into the blastof gas. The gasemployed for this purpose may be any gas which is not reacted uponeither by the amine or the hy- As examples there may be mentioned air,carbon dioxide, nitrogen, helium, argon and the like.

As previously stated in connection with large scale apparatus theamineis passed into the reaction chamber as a vapor or in an atomizedcondition at such a temperature that the reaction between'it thehydrohalide gas takes place in a zone above the vaporization point ofthe amine. The reactions herein described are exothermic and some of theheat necessary to bring the reaction zone to its proper temperature maybe supplied by the reaction itself When the process is being operatedentirely in the vapor phase the level ofthe amine in the reservoir iskept below the bottom of the line leading to the reaction chamber. frompassing outthrough this line into the reaction chamber. In someinstances it is desirable .to'mainta in the temperature of the amineevaporator above the vaporization point of the amine in'which case theamine is vaporized as soon as .it enters the chamber and passes on outinto the reaction chamber. This type of evaporation vessel is usuallyreferred toas a flash evaporator. To

aid in further understanding the invention, the following examples aregiven.

7 Example I During aperiod of onehour 90 parts of vaporized pyridinefrom a flash evaporator maintained at 266 C. and Z5 parts of hydrogenchloride gas were passed into a reaction chamber maintained at about 220C. l The resultant pyridine hydro- In this way any liquid is preventedchloride collected as a liquid. After cooling it solidified into acrystalline mass.

Example II One hundred (100) parts of aniline were placed in a containerand atomized by means of an air jet. A force feed was not used. Theatomized material was passed into a reaction chamber which hadpreviously been filled with dry hydrogen chloride gas. Clouds of anilinehydrochloride were formed. There was very little condensation in thereaction chamber, most of the fine hydrochloride being carried throughinto a condensing chamber to which it was connected. This was largelydue to the rapid entrance of the air which had been used foratomization. The yield was quantitative and the amine hydrochloride wasproduced in the form of very fine white crystals.

Example III Example .I V

While maintaining the reaction chamber at 240 C.-60 C., 45 parts ofaniline vapor were passed thereinto during a period of 30 minutes. Overthe same period 35 parts of hydrogen fiuoride vapors were also added.There was recovered a white solid which was identified as anilinehydrofiuoride. A portion of the product changed to a liquid uponexposure to moist air.

Example V One hundred (100) parts of hydrogen bromide, parts of nitrogenand 125 parts of di-n-butylamine vapor were passed into the reactionchamber which was maintained at 200 C.-240 C. About 200 parts of whitedi-butyl-amine hydrobromide were collected.

Example VI With the reaction chamber at a temperature of 225 C.-240 C.there was passed into it 125 parts or" di-n-butyl-amine vapor and 30parts of hydrogen fluoride vapor over a period of one hour. Whitedi-butyl-amine liydrofluoride formed.

Example VII One hundred (100) parts of N-butyl-amine were atomizedaccording to the process set out in Example III. A quantitative yieldwas obtained.

Example VIII A quantitative yield of ortho-toluidine hydrochloride wasobtained when 100 parts orthotoluidine were atomized according to theprocess described in Example III. Very desirable results were obtainedwhen the air for atomization had been preheated.

Example IX Ortho-toluidine was placed in an evaporator and heated sothat it was vaporized at the rate of about 100 parts (by Weight) perhour into the reaction chamber. At the same time, substantially dryhydrogen chloride gas was being added to the reaction chamber at therate of 50 parts (by w i ht) per hour. The operation was carried out forabout, nine'hours. Clouds of orthotoluidine were formed.

There was substantially no condensation in the reaction chamber, most ofthe fine hydrochloride settled out in the condensing chamber into whichit passed. The yield was essentially quantitative and the hydrochloridewas produced in the form of small white crystals.

Example X When 100 parts of piperidine were atomized according to theprocess set out in Example III, a quantitative yield of thehydrochloride was obtained.

Example XI Quantitative yields were obtained by atomizing ethyl-anilineby the process described in Example III.

Example XII With di-butyl-amine atomized and treated as described inExample III, a quantitative yield of its hydrochloride was obtained.

Example XIII One hundred (100) parts of aniline were atomized by meansof a forced feed and a nozzle (no atomizing gas jet being used). Theatomized material was passed into an atmosphere of dry hydrogen chlorideand a quantitative yield of aniline hydrochloride was obtained.

This invention is not limited to any group or class of amines but isapplicable to all organic bases capable of forming a stable dryhydrohalide. The amine nitrogen atom may be primary, secondary ortertiary. It may be attached to an acyclic, carbocyclic or heterocyclicnucleus and may be a ring member of a cyclic compound. As examples ofamines to which the application of the process herein described meritsspecial mention, there may be listed: benzyl-amine, n-propyl-amine,n-butyl-amine, ortho tolu benzyl amine, di-'nbutyl-amine,di-benzyl-amine, trimethyl-amine, tri-ethyl-amine,beta-phenyl-ethyl-amine, alpha-phenyl-ethyl-amine,beta-naphthyl-ethyl-amine, ethyl-aniline, methyl-aniline,ortho-toluidine, meta-toluidine, methyl-amine, para-toluidine,alpha-naphthyl-ethyl-amine, aniline, ortho-anisidine, ethyl-amine,para-phenetidine, benzyl-aniline, b:b'-di-naphthylamine,alpha-naphthylamine, beta-naphthylamine, alphaamino-anthraquinone,beta-amino-anthraquinone, 1:5-di-amino-anthraquinone, 1l-di-aminoanthraquinone, 1:3 di-amino anthraquinone, piperidine,pyridine, ortho di amino benzene, meta-di-amino-benzene, nicotine,quinoline, cyclo-hexyl-amine, morpholine, para-phenylene-diamine,aliphatic amino acid esters, glycinemethyl-esters, glycine ethyl esters,amino diphenyl-amine, di amino di phenyl-amine, diethanolamine,xylidines, amino-phenols, aminoquinolines, para-phenyiene-di-amnie, dianisidine, benzidine, amino-di-phenyl, amino-naphthol, pyrrole,guanidine, amino-benzoic acid and amino-naphthoic acid. Limited only byits contribution to the instability of the basic derivative or itshydrohalide any substituent for example, halogen, hydroxyl, nitro andcarboxyl may be attached to the nucleus treated.

As will be clear from the above, the particular temperature at which thereaction is carried out depends upon the particular amine and/or itshyrohalide. The vaporization point of the amines and their hydrohalidescovers a wide range of n-Propyl amine 4=9 Piperidine; 106 Benzyl-amine184 Aniline 184; Ortho-t'oluidine i 199 Methyl-amine hydrochlorida; 230Ortho-toluidine hydrochloride 242 Aniline hydrochloride 245Meta-toluidine hydrochloride -s; 250 Para-toluidine hydrochloride 257Para-phenylene-di-amine 267 Beta-naphthylamine 306 Di-ethyl-aminehydrochloride-ah 339 b:b-Di-naphthy1amine .471

In some instancesit may be desirable to oper ate at temperaturesslightly in excess of the acquite widely.

1 tual vaporization point of the amine or its by drohalide. Aniline isverysatisfactorily treated at temperatures slightly above .its boilingpoint, ior'example, 185C. to 20090.01 at temperatures slightly above theboiling point of its hydrochloride, for example 247 C; o'r250 C. to 260C.

Orthotoluidine is desirably treated within such temperature ranges as200C. to 210 C. and 245 C. to 270 0. Where no particular advantage is tobegained by carrying the amine hydrohalide a great distance from thereaction zone, tem peratures in the vicinity of but in excess of theboiling point of the amine may beused advantageously. So far as nowappears the only limiting factors in the matter of temperature are thestabilities of the organic base and its. hydrohalide. In all cases thelower temperature limit is at the vaporization point of the amine andthe upper temperature limit is that where decomposition of the amine orits hydrohalide renders the process uneconomical.

The range of compounds which may be satisfactorily treated may beextended over that ordinarily practical by such 'expedients assubatmospheric and superatmospheric pressures, temperatures above andbelow ordinary temperatures, gas-tight apparatus, dehydrating conditionsand the like. a I As previously indicated the'method of atomizing andthe degree of atomization may be varied other gas over an openingthroughwhich the liquid amine is drawn or forced. Proper adjustment of theatomizing gasjet avoids the neces sity for forced flow of the amine.Such a modification of the process is not ordinarily used since foratomizing is preheated the accompanying va-' porization is facilitatedand more completely attained. If desired the amine may be vaporizedcompletely in this manner and the vapor passed into the hydrogen halideatmosphere.

1 The mixing or contacting chamber is held at a temperature at or abovethe vaporizing temperature of the basic derivative in the preferredprocedure. Collection of the product in a separate chamber isfacilitated by maintaining the mixpresent.

the reaction chamber.

It has been found practical tov obtain the atomization by forcing a jetof air or r ing'chamber at ahigher temperature than that necessaryforthe vaporization of the particular hydrohalide formed.

.The proportions of the reacting components may be varied over a widerangeto obtain any desired result but for efficientoperation and highpurity of the product it is usually desirable to maintain the hydrogenhalide present in" at least the theoreticalproportions.

Throughout the specification and claims, the term hydrogen halide isused to denote anhydrous hy'drogen halide and the term hydrohalide acid!is used todenote the aqueoussolu tion of the hydrogen halide. 1 IBy-atomized material is meant a gas sus-' pension of liquid particlesand the term is used to include any vaporized material which may beformed in the atomization process described. ,While the process abovedescribed has'been treated as an anhydrous process, it is not intendedto indicate-that the presence of small amounts of water preventstheprocess from being commercially practical.

Forlarge scale apparatus it is desirable to use corrosion-resistantmaterial. For the vaporizer or tantalum have been found suitable.functions satisfactorily for the lining of the collection orcondensation chamber. In small scale apparatus glass or the like may beused satisfactorily excepting when hydrogen, fluoride is Where the aminehydrohalide formed'is a liq-i uid it may be desirable to appropriatelymodify the storage chamber in which it is received from Theprocessesherein described have the advantage .of producing amine hydrohalides byclean-cut extremely rapid and quantitative procedures. They have thefurther advantage that they can be applied to the preparation of organicbase hydrohalides heretofore impossible of preparation because of theirinstability to water. As many apparently widely different embodiments ofthis invention may be made without departing from the spirit and scopethereof, it is to be understood that I do not limit myself to thespecific embodiments thereof except as defined in the appended claims.

I claim: a V

1. The 'process'which comprises contacting an atomized amine and ahydrogen halide gas at a temperature not exceeding 471 C.

2; The process: which comprises contacting a va'porizedamine and ahydrogen halide gas at aternperature not exceeding 471 C.

3. The process which comprises contacting an atomized amine and ahydrogen halide gas inwhioh the contact takes place in a zone whosetemperature is in excess of the boiling point of the amine but below atemperature which will result in failure to form the corresponding aminehydrohalide said upper temperature limit in no 'case exceeding 471 C.

. perature which will result in failure to'form the corresponding. aminohydrohalide said upper temperature limit in no case-exceeding 471 C.

5. The process which comprises contacting a vaporized amine and ahydrogen halide gas in which the contact takes place in a zone whosetemperature isin excess oiwthe boiling point of the amine hydrohalideformed but below a temperature which will result infailure to form thecorresponding amine hydrohalide said upper temperature limit in no caseexceeding 471 C.

6. The method of making an aromatic amine hydrohalide which comprisesreacting in the vapor phase an aromatic amine and a hydrogen halide saidreaction being carried out at temperatures not exceeding 471 C.

7. The method of making an ortho-toluidine hydrohalide which comprisesreacting in the vapor phase ortho-toluidine and a hydrogen halide saidreaction being carried out at temperatures not exceeding 270 C. a

8. The method of making ortho-toluidine hydrochloride which comprisesreacting in the vapor phase ortho-toluidine and hydrogen chloride saidreaction being carried out at temperatures not exceeding 270 C.

9. The method of making anaromatic amine hydrohalide, which comprisesreacting in the vapor phase and at a temperature below 250 C.

between an aromatic amine and a hydrogen halide.

10. In the process of preparing an anhydrous amine hydrochloride, thestep which comprises passing an anhydrous amine vapor into dry hy drogenchloride gas at a temperature not greater than 471 C.

11. The method of making an aromatic amine hydrohalide, which comprisesreacting in the vapor phase and at a temperature below a tem peraturewhich will result in failure to form the corresponding aminehydrohalide, between an aromatic amine and a hydrogen halide saidreaction being carried out at temperatures not exceeding 471 C.

12. The method of making ortho-toluidine hydrochloride which comprisesreacting in the vapor phase but below a temperature which will result infailure to form ortho-toluidine hydrochloride, ortho-toluidine and.hydrogen chloride said reaction being carried out within the temperaturerange 245 C. to 270 C.

13. The method of making an ortho-toluidine hydrohalide which comprisesreacting in the vapor phase but below a temperature which will result infailure to form the corresponding orthotoluidine hydrohalide,artho-toluidine and a hydrogen halide said reaction being carried outwithin the temperature range 245 C. to 270 C.

ARTHUR LAWRENCE FOX.

CERTIFICATE OF CORREQTWN.

Patent No. 2,007,l89. July 9. 1935.

ARTHUR LAWRENCE P6X.

it is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 3,second column, line 5,ior "atomizattion" read atomization; page 5,second column, line 71, claim 4, for "amino" read amine; and page 6,second column, line 23, claim 13, for "artho-tolnidine" readortho-toluidinc; and that the said Letters Patent should be read withthese corrections therein that the same may conform to the record of thecase in the Patent Office.

Signed and sealed this 8th day of October, A. D. 1935.

Les 1 ie Frazer (Seal) Acting Commissioner of Patents.

